Process for breaking petroleum emulsions employing certain oxyalkylated amine-modified thermoplastic phenolaldehyde resins



United tates Melvin De Groote, University City,

Petrolite Corporation, of Delaware No Drawing. Application March 25,1954 Serial No. 418,785

Claims. (Cl. 252344) Mo., assignor to Wilmington, Del., a corporationThe present invention is a continuation-in-part of my co-pendingapplication, Serial No. 398,631, filed December 16, 1953, now abandoned.

This invention relates to processes or procedures particularly adaptedfor preventing, breaking or resolving emulsions of the water-in-oiltype, andparticularly petroleum emulsions.

My invention provides an economicaland rapid process for resolvingpetroleum emulsions of the water-in-oil type that are commonly referredto as cut oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the invention.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value inremovingimpurities, particularly inorganic salts, from pipeline oil.

Attention is directed to my co-pending application, Serial No. 398,631,filed December 16, 1953, which relates to a process for breakingpetroleum emulsions employing a demulsifier including products obtainedby condensing certain phenol aldehyde resins, therein described indetail, with certain basic secondary amines, also therein described indetail, and pyruvic aldehyde.

The present invention may be characterized in that it is concerned witha process for breaking petroleum emulsions employing demulsifiersincluding the above described reaction products of Serial No. 398,631further oxyalkylated by means of certain monoepoxides, hereinafterdescribed in detail.

The products obtained by oxyalkylation with a monoepoxide such asethylene oxide, propylene oxide, butylene oxide or the like, can besubjected to further reaction with a product having both a nitrogengroup and 1,2- epoxy group, such as 3-dialkylaminoepoxypropane. See U.S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid washing atent of building stone and brick; aswetting agents and spreaders in the application of asphalt in roadbuilding and the like; as a flotation reagent in the flotationseparation of various aqueous suspensions containing negatively chargedparticles, such as sewage, coal washing waste water, and various tradewastes and the like; as germicides, insecticides, emulsifying agents,as, for example, for cosmetics spray oils, water-repellent textilefinishes; as lubricants, etc.

In the present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethyleneglycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofXylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases or vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

Reference is made to U. S. Patent 2,499,368 dated March 7, 1950, to DeGroote and Keiser. Attention is directed to that part of the text whichappears in columns 28 and 29, lines 12 through 75, and lines 1 through21, respectively. Reference is made to this test with the same force andelfect as if it were herein included. This, in essence, means that thepreferred product for resolution of petroleum emulsions of thewater-in-oil type is char acterized by the fact that a fifty-fiftysolution in Xylene, or its equivalent, when mixed with one to threevolumes of water shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be dividedinto five parts:

Part 1 is concerned with phenol-aldehyde resins suitable forcondensation;

Part 2 is concerned with suitable secondary amines which can be employedin conjunction with the resins in the condensation procedure;

Part 3 is concerned with the condensation procedure as such;

Part 4 is concerned with reactions involving the intermediates obtainedin the manner described in Part 3, preceding, and certain alpha-betamonoepoxides having not over 4 carbon atoms;

Part 5 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products.

PART 1 This part is concerned with the preparation of phenolaldehyderesins of the kind described in detail in U. S. Patent No. 2,499,370,dated March 7, 1950, to De Groote and Keiser, with the followingqualifications; said aforementioned patent is limited to resins obtainedfrom di- 3 functional phenols having 4 to 12 carbon atoms in thesubstituent hydrocarbon radical. For the present purpose the substituentmay have as many as 18 carbon atoms, as in the case of resins preparedfrom tetradecylphenol, substantially para-tetradecylphenol, commerciallyavailable. Similarly, resins can be prepared from hexadecylphenol oroctadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to thefollowing U. S. Patents: Nos. 2,499,365, 2,499,366, and 2,499,367, alldated March 7, 1950, to De Groote and Keiser. These patents, along withthe other two previously mentioned patents, describe phenolic resins ofthe kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are mostsatisfactory, with the additional C carbon atoms also being verysatisfactory. The increased cost of the C and C carbon atom phenolrenders these raw materials of less importance, at least at the presenttime.

Patent 2,499,370 describes in detail methods of preparing resins usefulas intermediates for preparing the products of the present application,and reference is made to that patent for such detailed description andto Examples 1a through 103a of that patent for examples of suitableresins.

As previously noted, the hydrocarbon substituent in the phenol may haveas many as 18 carbon atoms, as illustrated by tetradecylphenol,hexadecylphenol and octadecylphenol, reference in each instance being tothe difunctional phenol, such as the orthoor para-substituted phenol ora mixture of the same. Such resins are described also in issued patents,for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to DeGroote and Keiser, such as Example 710:.

Reference has been made to an earlier formula which was in essence anover-simplification representing a phenol-formaldehyde resin. Actually,some other aldehyde, such as acetaldehyde, propionaldehyde, orbutyraldehyde, may be used. The resin unit can be exemplified thus:

R R n R in which R' is the divalent radical obtained from the particularaldehyde employed to form the resin.

As previously stated, the preparation of resins of the kind hereinemployed as reactants is well known. See U. S. Patent No. 2,499,368,dated March 7, 1950, to De Groote and Keiser. Resins can be made usingan acid catalyst or basic catalyst or a catalyst showing neither acidnor basic properties in the ordinary sense, or without any catalyst atall. It is preferable that the resins employed be substantially neutral.In other words, if prepared by using a strong acid as a catalyst, suchstrong acid should be neutralized. Similarly, if a strong base is usedas a catalyst, such strong acid should be neutralized. Similarly, if astrong base is used as a catalyst it is preferable that the base beneutralized although we have found that sometimes the reaction describedproceeded more rapidly in the presence of a small amount of free base.The amount may be as small as a 200th of a percent and as much as a fewtenths of a percent. Sometimes moderate increase in caustic soda andcaustic potash may be used. However, the most desirable procedureinpractically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins We found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purpose of convenience suitable resins arecharacterized in the following table:

TABLE I Moi. wt Ex- Position R of resin ample R of R derived n moleculenumber from (based on n+2) 1a Phenyl Para- Formal- 3. 5 992. 5

2a Tertiary butyl 3. 5 882. 5 Secondary butyL 3. 5 882. 5 Cyclo-hexyl.3. 5 1,025. 5 Tertiary amyl. 3. 5 959. 5 Mixed second 3. 5 805. 5

and tertiary amyl. Propyl 5 805. 5 Tertiary hexyl 5 1. 036. 5 Octyl .51,190.5 5 1, 267. 5 5 1, 344. 5 Dodecyl .5 1, 498. 5 13a Tertiary butyl5 945. 5

14a Tertiary amyl 5 1,022. 5 15a Nonyl 5 1, 330. 5 16a Tertiary butyL 51, 071. 5

Tertiary amyl 5 1,148. 5 onyl 5 1, 456. 5 Tertiary butyl. 5 1,008. 5

Tertiary amyl 5 1,085. 5 Nonyl 5 1, 393. 5 Tertiary butyl 2 996. 6

Tertiary amyl 2 1, 083. 4 Ony 2 1, 430. 6 Tertiary butyL 8 1, 094. 4Tertiary amyl. 8 1. 189. 6 l 8 1, 570. 4 5 604. 0 5 646. O 5 653.0 5688.0

PART 2 As noted previously, a variety of secondary amines free from aprimary amino group may be employed. These amines fall into fivecategories, as indicated previously.

One category consists of strongly basic secondary monoamides free fromhydroxyl groups whose composition may be indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl. radicaland may be heterocyclic in, a few instances as in the case of piperidineand a secondary amine derived from furfurylamine by methylation orethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readilyavailable are, of course, amines suchas dimethylamine, methylethylamine, diethylamine, dipropylamine,ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine,and dinonylamine. Other amines include bis(l,3-dimethyibutyl) amine.There are, of course, a variety of primary amines which can be reactedwith an alkylating agent such as dimethyl sulfate, diethyl sulfate, analkyl bromide, an ester of sulfonic acid, etc., to produce suitableamines within the herein specified limitations. For example, one canmethylate alpha-methylbenzylamine, or benzylamine itself, to produce asuitable reactant. Needless to say, one can use secondary amines such asdicyclohexylamine, dibutylamine or amines containing one cyclohexylgroup and one alkyl group, or one benzyl group and one alkyl group, suchas ethylcyclohexylamine, ethylbenzylamine, etc.

Other suitable compounds are exemplified by Other somewhat similarsecondary amines are those of the composition as described in U. S.Patent No. 2,375,659, dated May 8, ,1945, to Jones et al. In the aboveformula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation of similar primary amines, or, for that matter, aminesof the kind described in U. S. Patent No. 2,482,546, dated September 20,1949, to Kaszuba, provided there is no negative group or halogenattached to the phenolic nucleus. Examples include the following:beta-phenoxyethylamine, gamma-phenoxypropylamine,beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No.456,517 and may be illustrated by The secondary category representssecondary amines which are hydroxylated monoamines. These may beillustrated by diethanolamine, methylethanolamine, dipropanolamine,dibutanolamine and ethylpropanolamine. Suitable primary amines which canbe so converted into secondary amines include butylamine, amylamine,hexylamine, higher molecular weight amines derived from fatty acids,cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include 2-amino-1-butanol, 2- amino 2methyl-l-propanol, Z-amino-Z-methyl-l,3-propanediol,2-amin0-2-ethyl-1,3-pr0panediol, and tris-(hydroxylmethyl)-aminoethane.Another example of such amines is illustrated by4-amino-4-methyl-2-pentanol.

Other suitable compounds are the following:

HOCzH4 or comparable compounds having two hydroxylated groups ofdifierent lengths as in nocniomocmomoomom /NH HOCaHA Other examples ofsuitable amines include alpha-methylbenzylamine and monoethanolamine;also amines obtained by treating cyclohexylmethylamine with one mole ofan oxyalkylating agent as previously described;betaethylhexylbutanolamine, diglycerylamine, etc. Another type of aminewhich is of particular interest because it includes a very definitehydrophile group includes sugar amines such as glucamine, galactamineand fructamine, such as N-h'ydroxyethylglucamine,N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by See, also, correspondinghydroxylated amines which can be obtained from rosin or similar rawmaterials and described in U. S. Patent No. 2,510,063, dated June 6,1950, to Bried. Still other examples are illustrated by treatment ofcertain secondary amines, such as the following, with a mole of anoxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine,phen'oxyalphametnylethylamine, and phenoxypropylamine.

Polyamines free from a hydroxyl group may be illustrated by thefollowing:

OHa /C a HCaH4NO2H4N H H H CzHa /C2 5 /N C zHaNC 2H4N H CH CHa on. or: 5

\ H NpropyleneNpropyleneN CH3 C N C 2H4N 02 4 H 0 0 2H C 2H4 OH (H 002114) rNCzHtgcz t (C 2 4 03H I I N C 'tH4N C rHiN H O 01H 02H 0 If N C2114 O C 2H4 H O C 2114 C 2114 O H 40 N C 2114 O C 2H4N H O C 2114 C :H40 H CH3 0 H: H

N propyleneNpropyleneN H O C 7H4 C H4 O H 0 H3 0 H3 NC2 4NC2 4 C2H4N H HH O C 2H4 C :11; O H

CH3 CH3 N CzH4N CfiiNCzHtNCfir H H H 1100,11 (hEhOH H O C1114 02H; 0 H

N CzH4N C2H4NCzH4N O2H4N H H H CH3 CH:

Suitable cyclic amidines which may or may not have a hydroXyl group butare free from primary amino groups may be illustrated by the following:

1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazolineZ-heptadecyl,l-methylaminoethyl tetrahydropyrimidine4-me'thyl,2-dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine Acompound having no basic secondary amino radical but "a basic primaryamino radical can be reacted with a mole of an alkylene oxide, such asethylene oxide, propylene oxide, glycide, etc., to yield a perfectlysatisfactory reactant for the herein described condensation procedure.This can be illustrated in the following manner by a compound such asN-CHg CnEss-C N-CH:

C2H4.NH1 2-heptadecyl,l-aminoethylimidazoline which can be reacted witha single mole of ethylene oxide, for example, to produce the hydroxyethyl derivative of Z-heptadecyl,l-aminoethylimidazoline, which can beillustrated by the following formula:

Other reactants may be employed in connection with an initial reactantof the kind described above, to wit,Z-heptadecyl,l-aminoethylimidazoline; for instance, reaction with analkylene imine such as ethylene imine, propylene imine, etc. If reactedwith ethylene imine the net result is to convert a primary amino radicalinto a secondary amino radical and also introduces a new primary aminegroup. If ethylene imine is employed, the net result is simply toconvert Z-heptadecyl,l-aminoethylimidazoline intoZ-heptadecyl,1-diethylenediamineoimidazoline. However, it propyleneimine is used the net result is a compound which can be considered asbeing derived hypothetically from a mixed polyalkylene amine, i. e., onehaving both ethylene groups and a propylene group between nitrogenatoms.

PART 3 The products obtained by the herein described processes representcogeneric mixtures which are the result of a condensation reaction orreaction-s. Since the resin molecule cannot 'be defined satisfactorilyby formula, al-

though it may be so illustrated in an idealized simplifi cation, it isdifficult to actually depict the final product of the cogeneric mixtureexcept in terms of the process d obvious that the procedure becomescomparatively simple. Indeed, perhaps no description is necessary overand above what has been said previously, in light of subsequentexamples. However, for purpose of clarity the following details areincluded.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact, usually it is apt to be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, we have found it convenient to use a solvent andparticularly one which can be removed readily at a comparativelymoderate temperature, for instance, at 150 C. A suitable solvent isusually benzene, xylene or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are notsoluble except in oxygenated solvents or mixtures containing suchsolvents are not here included as raw materials. The reaction can beconducted in such a way that the initial reaction, and perhaps the bulkof the reaction, takes place in a polyphase system. However, ifdesirable, one can use an oxygenated solvent such as a low-boilingalcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use a comparatively non-volatile solvent such asdioxane or the diethylether of ethyleneglycol. One can also use amixture of benzene or xylene and such oxygenated solvents. Note that theuse of such oxygenated solvent is not required in the sense that it isnot necessary to use an initial resin which is soluble only in anoxygenated solvent as noted, and it is not necessary to have a singlephase system for reaction.

Pyruvic aldehyde is available as a 36% aqueous solution. In this way itis comparable to formaldehyde which is available as a 37% aqueoussolution, and is sometimes used in more dilute form. I have found nodifficulty in promoting the condensation reaction although at times itis desirable to add some solvent having a common solvent effect. Thus anoxygenated solvent may or may not be employed. Such solvent may beemployed in combination with a hydrocarbon solvent such as xylene.However, if the reaction mass is going to be sublected to some furtherreaction where the solvent may be objectionable as in the case of ethylor hexyl alcohol, and if there is to be subsequent oxyalkylation, then,obviously, the alcohols should not be used or else they should beremoved. The fact that an oxygenated solvent need not be employed, ofcourse, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether ornot the cogeneric mixture obtained at the end of the reaction is to beused as such or in the salt form. The cogeneric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete removal. Even if one startswith a resin which is almost water-white in color, the condensationproducts obtained are invariably dark and particularly reddish or darkred in color.

By and large, the melting point of the condensate is apt to be higherthan of comparable condensates obtained by the use of formaldehyde orfurfural. As has been suggested previously, this apparently is due tothe difunctional property of pyruvic aldehyde. Indeed, depending on theresin selected and the amine selected the condensate product or reactionmass on a solvent-free basis is apt to be harder than the original resinitself. This is particularly true when all the amino hydrogen atomspresent in the amine have entered into reaction.

The products obtained, depending on the reactants selected, may bewater-insoluble, or water-dispersible, of water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a 5% solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminate all solvent, using a temperature of not over C.and employing vacuum if required. This applies, of course, only to thosecircumstances where it is desirable or necessary to remove the solvent.Petroleum solvents, aromatic solvents, etc., can be used. The selectionof solvent, such as benzene, xylene, or the like, depends primarily oncost, i. e., the use of the most economical solvent and also on threeother factors, two of which have been mentioned previously; (a) is thesolvent to remain in the reaction mass without removal? (b) is thereaction mass to be subjected to further reaction in which the solvent,for instance, an alcohol, either low boiling or high boiling, mightinterfere as in the case of oxyalkylation? and the third factor is this(0) is an etfort to be made to purify the reaction mass by the usualprocedure as, for example, a water-wash to remove any unreacted lowmolal soluble amine, if employed and present after reaction? Suchprocedures are well known and, needless to say, certain solvents aremore suitable than others. Everything else being equal, we have foundxylene the most satisfactory solvent.

I have found no advantage in using a low temperature, approximately roomtemperature, at the start of the reaction although this is sometimesdone purely as a matter of convenience. Indeed, using pyruvic aldehyde Ihave usually done nothing more than prepare the reaction mixture, add asuitable amount of xylene, and reflux for approximately 3 to 6 /2 hoursat temperatures varying, as the case may be, from 135 to C. Where theamine has a comparatively low basicity I have sometimes added to smallamount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance, approximatelyparts of benzene and 35 parts of xylene, and a phase-separating trap toeliminate water, I have found that I could employ temperatures between90 and 100 C., and eliminate the water of condensation by refluxing atthis temperature. However, I have found no particular advantage in usingthis low temperature over and above the high temperature previouslynoted.

Example 1b The resin employed was the one previously designated as 28aand had a molecular weight of approximately 600. grams of this resinwere dissolved in slightly more than an equal weight of xylene and 61grams of di-isopropanolamine added. 61.5 grams of methyl glyoxal (36%aqueous solution) were added and the mixture stirred for about 30minutes and then the temperature allowed to rise to 144 C., where it wasallowed to reflux for 6.75 hours. During this refluxing period aphase-separating trap was used to remove the water of formation. At theend of this time the reaction was complete and the product was obtainedin the form of a xylene solution. A small sample was evaporated toeliminate the xylene. The resultant product was a highly viscous, tackymaterial, being black in color with a reddish tinge.

Similar products were prepared as indicated in the following table:

Methyl Solvent Max. Resin glyoxal (xylene Time temp. Ex.- No. amt.,Secondary amine Amt (36% aq unless period, during grams grams so1.),otherwise hrs. reaction,

grams noted), 0.

grams 175 Di-isopropauo1amine 61 61. 180 6. 75 144 150 Di-n-butylamine65 50. 0 165 6. 5 158 150 Di-ethylamine 37 50. 0 156 5. 5 145 150Di-eyclohexylarnine- 91 50. O 153 6. 168 300 Morpholine 87 100. 0 310 5.75 143 300 Di-2-ethylhexylnmine. H. 241 100. 0 288 5. 00 165 225Bis-(1,3-dimethy1butyDa Be 139 75. 0 237 225 Dl-isopropanolamine 75. 0233 3. 5 165 225 a-Methylbenzylethanolamine 124 75. 0 238 3. 5 160 225Dl-ethanolamine 79 75. O 230 3. 0 161 225 Aminoethyl ethano1am1ne.. 7875. 0 235 2. 5 145 225 Diethanolalnlne 79 75.0 "55470 3. 5 225 0 79 75.055-170 3. 5 100 225 do 131. 5 133. 0 "55470 3. 5 101 225Diisopropanolamlne. 174 133. 0 240 2. 0 236 61 61. 5 238 7. 5 197 6550.0 195 6. 5 165 197 37 50.0 205 5. 5 150 197 91 50. 0 180 6. 75 393 87100 380 7. 0 393 Dl(2-ethylhexyl)arnine. 241 100 399 5. 75 65 197N-methylaniline 54 50. 0 101 4. 5 168 295 169 75. 0 303 5. 0 160 295Dl-lsopropanolamine 100 75. 0 205 3. 75 160 225 Di-ethanolarnlne- 79 75.0 300 3. 0 140 188 Di-isopropylamlne 61 61. 5 222 7. 75 166 188Dl-n-butylamlne.- 65 50. 0 180 6.0 150 188 Di-ethylamine 37 50.0 178 6.5 162 374 Di-cyclohexylamihe. 91 50. 0 194 7. 5 160 374 Morpholine 87100 374 7. 0 170 188 Di-(2-ethylhexyl)amine. 241 100 379 5.0 165 280N-methylaniline 54 50 200 6. 0 168 280 Di-(beta-phenvlethyl)amine- 16975 295 6. 5 155 280 D1-1sopropan0lamine 100 75 273 4. 0 158 280Di-ethanolamine 79 75 273 3. 0 155 No'rE.-In the above examples nocatalyst was added. In some duplications of the above small amounts ofcatalyst were added up to 1% to 2% of either powdered caustic soda orpowdered sodium methylate. No advantage was noted in the use of acatalyst provided the amine was sufficiently basic.

In Examples 12b, 13b and 14b indicated by the double asterisk thesolvent was a mixture of 170 parts of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except inExamples 14b and 155 where the ratio was 1 to 3.5 to 1.75 in bothinstances.

In Examples lb through 15b the resin employed was the one identified asExample 28a. In Examples 16b through 25b the resin employed was the oneidentified as Example 32a, and in Examples 26b through 35b the resinemployed was identified as Example 39a.

Returning now to consideration of the structure of the condensate itbecomes obvious that one could obtain ring compounds. Using theabbreviated formula previously applied, the simplest ring could be shownthus:

Obviously, one could have rings with a larger number of members in thering to say nothing of complications involving alkanol radicals, forinstance, the elimination of a hydrogen atom from the alkanol hydroxylgroup. Furthermore, the situation becomes even more complicated if theratios are changed to correspond to ratios described in my co-pendingapplication, Serial No. 376,240, filed August 24, 1953, now Patent No.2,792,365 dated May 14, 1957. In this particular instance there aredescribed a number of complicated condensates in which 3 /2 moles ofdieth'an'olamine, or the like, 3 /2 moles of formaldehyde, and one moleof the phenol-aldehy'cle' resin, are employed. If correspondingcondensates are prepared, rcplacing"3' /2" moles' of formaldehyde by 1%niole's' ofpyruvic aldehyde,-a variety of compounds are obtained whichhave unusual structure but are still organic solvent-soluble andsusceptible to oxyalkylation. Indeed, another variety of somewhat morecomplicated materials are obtained by using as the amine reactantdi(hydroxyethyl)N,N'-ethylene diamine having the following structure:

HO 01H; E.

An initial product can be made treating the amine as if it were nothingmore than a hydroxylated monoamine. Subsequently pyruvic aldehyde may beadded up to, for example, the amount originally employed with theproduction of linear polymers and in some instances cross-linking. It isunderstood that regardless of what amine is used the final productobviously is, and must be, organic solvent-soluble. The primaryobjective is to obtain a condensate which is organic solvent-soluble andnot an infusible resin. Such condensate is particularly valuable foroxyalkylation. The products so obtained find utility in various arts.

See my co-pending application, Serial No. 383,928, filed October 2,1953, now Patent No. 2,792,366 dated May 14, 1957. This particularapplication is essentially the same as the instant application exceptthat glyoxal is used instead of pyruvic aldehyde. It is well known thatpyruvic aldehyde combines with alcohols to form dialkyl and tetra-alkylacetals. There is some indication that polymerization may take place orat least some reaction involving one of the hydrogens of the methylradical; all of which simply is an indication of a more complicated typeof reaction which may take place under certain conditions when pyruvicaldehyde (methylglyoxal) is used in comparison to glyoxal.

PART 4 At the present time there are available a number of alkyleneoxides, particularly ethylene oxide, or propylene oxide and butyleneoxide, either as a single isomer or-as a mixture of isomers. Glycide isavailable, or readily prepared. The same applies to methylglycide.

Oxyalkylation with any of the aforementioned alkylene oxides iscomparatively simple, in light of present day atlases knowledge. Infact, it is stated briefly in U. S. Patent No. 2,636,038, dated April21, 1953, to Brandner, in the following language: The compounds arepreparel by the addition reaction between alkylene oxides andsubstituted oxazolines of the group named hereinbefore. The additionreaction is advantageously carried out at elevated temperature andpressure and in the presence of an alkaline catalyst.

As to a more complete description of oxyalkylation procedure referenceis made to U. S. Patent 2,629,706, dated February 24, 1953, to De Grooteand Keiser. See particularly the subject matter which appears in column7 of said patent.

Propylene oxide and butylene oxide react somewhat more slowly thanethylene oxide and may require a somewhat higher temperature, somewhatgreater agitation, or an increased amount of alkaline catalyst, such asfinely powdered sodium hydroxide or sodium methylate. If the product tobe subjected to oxyalkylation is xylenesoluble or soluble in any one ofa number of inert solvents, there is no particular ditiiculty involved.The same is true if the product is a liquid at oxyalkylationtemperatures. If it is not soluble or a liquid then in some casesinitial oxyalkylation can be accomplished by means of an alkylenecarbonate, such as ethylene carbonate or propylene carbonate which has asolubility effect as well as acting as an oxyalkylation agent. As soonas a suitable product is obtained by the use of a carbonate furtherreaction can be completed with the oxide. An alternate proceduresometimes employed with insoluble materials is to reduce the products toan extremely finely ground powder and oxyalkylate during suspensionusing particularly vigorous agitation.

All these procedures have been described repeatedly in the literatureand, as a matter of fact, suitable operational directions are availablefrom any one of several makers of alkylene oxides.

Example 10 Due to their ready availability, the bulk of theoxyalkylation derivatives were prepared from ethylene oxide, propyleneoxide, butylene oxide, or a mixture of the same. Generally speaking, theautoclaves or oxyalkylators em ployed ranged from approximately 2gallons in size to approximately gallons in size. The general procedurewas to start with a fairly small sample; for instance, approximately2000 grams, of the product to be oxyalkylated and 1000 grams of asolvent such as xylene, or a highboiling aromatic solvent, or thediethylether of ethyleneglycol, or a mixture of these solvents. Powderedcaustic soda, or sodium methylate, were added as a catalyst in an amountgenerally not over 2%, and more catalyst was added if the amount droppedto /2% or less. Initial oxyalkylation generally started by adding 50% byweight, 100% by weight, 200% by weight, 300% by weight, 500% by weight,etc., until at least ten times as much oxide had been added, at least insome examples. Excellent compounds or suitable raw materials have beenobtained by adding as much as 50 parts by weight of oxide to one part ofthe initial reactant. In some instances the same examples were repeatedand then reacted with one or more oxides; for instance, in the tablewhich follows there are examples where an oxyethylated product wasoxypropylated subsequently, or vice-versa. Comparatively small samples,for instance, one to five grams, were taken at various stages and testedfor emulsifiability factor and also for demulsifying effect on crude oilemulsions. The tabular data do not reflect the slight discrepancy due tothe sample withdrawal.

More specifically then, 15 pounds (6,500 grams) of the condensatepreviously identified as Example 115, were mixed with an equal weight ofsolvent (being xylene in this series). The mixture was placed in a smallautoclave together with one and one-half pounds (675 grams) of finelypowdered caustic soda, and-stirred, and the temperature raised toapproximately -130 C. 5 pounds (2270 grams) of ethylene oxide were addedin approximately 30 minutes. The pressure during the oxyalkylation wasabout 10 to 15 pounds per square inch. The resultant product was a fiuidhaving a reddish black cast. Except for the withdrawal of a few gramsfor examination, the product was then subjected to further oxyalkylationwith another 5 pounds of ethylene oxide and without the addition of anymore catalyst or any more solvent.

Note what is said in regard to these examples and subsequent examples inthe text immediately following, and in the tables.

A number of additional examples appear in tabular form in the fivetables immediately following, to wit, Tables III, IV, V, VI and VII.These are self-explanatory, particularly in regard to the first threetables. The last two require a little more careful examination. This isdue to an effort to condense the data and not burden the text with anunduly large volume of detail.

Due to the fact that various size quantities are used the ratiossometimes appear in grams or kilograms and sometimes in pounds. Whenpounds are used the designation is included.

In Tables III, IV and V successive stages of oxyalkylation are shown.Small samples of a few grams were withdrawn and tested for solubilityand also for demulsification effectiveness. The withdrawal of such smallsamples was ignored. In some instances the example was repeated and usedsubsequently for reaction with one or more other oxides. In someinstances the product so obtained in the first stage of oxyalkylationrepresented a comparatively large quantity and was subdivided perhapsinto one-half or even a smaller fraction, and then this smaller fractiononly subjected to oxyalkylation with another oxide. As previously noted,no further explanation is required in regard to the first three tables.

In the fourth table, Table VI, it is to be noted that Example 1 isderived from Example 60. Referring to Example 60 it will be noted thiswas derived originally from oxyalkylation-susceptible compound Example1b. In Example 60, oxyalkylation-susceptible compound Example 1b hadalready been treated with ethylene oxide. Thus, in Table VI, althoughthe oxyalkylation-susceptible compound is properly designated as Example60 for the reason it is now the reactant subjected to oxypropylation,the oxyalkylation-susceptible compound as far as reference to weightgoes (in this instance 15 pounds) goes back to the original compoundExample 1b. This is obvious, and is even more obvious for the reasonthat it is subsequently emphasized in connection with the weight ratio,as explained subsequently.

It will be noted also that in the fourth column in Table VI the oxideused is marked as indicated and in each instance the oxide employed inthis second stake is shown, in two instances in Table VI being propyleneoxide and in one instance being ethylene oxide.

Bearing in mind what is said in regard to Example 1 being derived fromExample 60, which in turn was derived from Example 112 plus ethyleneoxide, it should be noted that this table does not, as far as the firstfour columns go, reflect the amount of oxide which was added in theinitial or earlier stage. As previously noted, this does not causeconfusion and, in fact, permits holding the data to a minimum in lightof what is said next.

Referring now to columns seven, eight, nine and ten which are concernedwith composition at the end, it will be noted that these data do takeinto consideration the amount of oxide added initially as well as theoxide during the second stage. Thus, although this shows the propyleneoxide added it also shows the original ethylene oxide as representingthe five-to-one weight ratio based on the oxyethylation of the firststage. This can be stated perhaps more simply in the following way: Oninitial examination the table shows that Example 1] was derived '15 fromExample 60. As to the composition of Example 60 one need only note thatin the seventh column it shows that 1125 grams of butylene oxide wereadded and the weight ratio to the oxyalkylation-susceptible compoundtabular presentation that yet has been developed after a considerableseries of experimentations, and reports in table form. This is true evenwhere three oxides were employed as for instance in Example 1g in TableVII.

Example 111 was .5 to 1, but it also shows that the weight 5 Example 1gwas obtained from Example Si in Table VI. ratio of the ethylene oxide atthe same stage was three Example 5], as indicated, was obtained by anoxypropylato one. Thus, without even checking back to a prior tion ofExample If, and Example 1]", as previously noted, table it is obviousthe initial material, Example 6c, subwas obtained from Example 60. Thepreparation of jected to a second oxyalkylation step, consisted of a 10Example from Example 1b has been discussed in conproduct in which onepound of the oxyalkylation-suscepsiderable detail In the previous text.Again it is to be tible compound was combined with 3 pounds by weightnoted that 1n the tables the ratios of the oxide to the of ethyleneoxide, prior to oxypropylation. initial product prior tooxyalkylation isshown so there Since 1125 grams of butylene oxide were used which is noquestion as to the composition of each example is equivalent to 2.7pounds, which was equivalent to one- 15 although considerable data havebeen presented in what half part by weight of theoxyalkylation-susceptible com- 1s a comparatively condensed and readilyunderstandable pound Example 1b, it means in essence that 5.4 poundsform. of the oxyalkylation-susceptible compound had previously Note whatis said in regard to the color of theprodbeen combined with three timesits weight of ethylene nets in the tables. For most industrial purposesthere oxide, i. e., 16.2 pounds of ethylene oxide and is now is noobjection to the color. The products can be debeing combined withone-half its weight, 2.7 pounds, of colorized by conventional procedure,using bleaching butylene oxide. Referring back to Example 6 it will beearths, filtering clays, charcoal, or the like. A trace or noted thatthe ratio of ethylene oxide to initial oxyalkylasmall amount ofcatalyst, if present, can be removed for tion-susceptible compound wasthree to one, most purposes by the mere addition of a comparable All thedata in Tables VI and VII are presented in the 25 amount of hydrochloncacid .or by any other suitable same way. We find this is the most simpleand concise means.

TABLE I11 Composition before-Amount of OSC, catalyst and solventconstant before and alter oxyalkyl- Composition at end Operatingconditions a 1011 Ex. Weight ratio End product-- No. Color and physicalOS 0 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 usedlyst. solvent used EtO to P10 to B to pres. temp, of re- No. grams EtONaOH, grams EtO oxyalkyloxyalkyloxyalkylp. s. 1. 0. action,

grams grams grams 1 ation ation atlon hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

15.0# 0 675 15 0# 5.0# 0.33 -130 Dark amber viscous llquld. 15. 0 5. 0#s75 15. 0 10. 0 .57 125-130 Do. 15. 0 10. 0 575 15. 0 15. 0 1. 0 125-130Do. 15. 0 15. 0 075 15. 0 20. 0 1. 33 125-130 Do 15.0 20.0 675 15.0 30.02.0 125.130 1% Very vlscous. 15.0 30.0 675 15.0 45.0 3.0 125-130 1%Heavy v 1scous.

7.5 22.5 337.5 7.5 30.0 4.0 125-130 1% Semi-fluid. 7. 5 30. 0 337. 5 7.5 45. 0 6.0 125-130 1 Do. 30.0 0 450 30.0 5.0 0.167 '125-130 M Greenishblack viscous liquid. 30.0 5.0 450 30.0 10.0 0.333 125-130 Do. 30. 0 10.0 450 30. 0 15. 0 0. 50 125-130 Do. 30. 0 .15. 0 450 30. 0 30. 0 1. 0125-130 1 Do. 15.0 15.0 225 15.0 30.0 2.0 125-130 1 Very viscous. 15. 030. 0 225 15. o 45. 0 3. 0 125-130 1% 130. 15c... 15.0 45.0 225 15.050.0 4.0 125-130 1% Seml-fiuld.

1 Oxyalkylation-susceptible compound. In some instances Weights changefrom gram basis to pound basis. Such change in unit 1s obvious.

TABLE IV Composition before-Amount oi OSO, cataiyst and solvent constantbefore and after oxyalkyl- Composition at end Operating conditions ationEx. Weight ratio End product-- No. Color and physical 080 1 Oxide Cata-Xylene Oxide Max. Max. Time state Ex. OSC 1 used lyst, solvent used EtOto PrO to BuO to pres. temp, of re- No. grams PrO NaOH, grams PrOoxyalkyloxyalkyloxyalkylp. s. 1. C. action,

grams grams grams 1 ation ation ation hrs.

suscept suscept. suscept.

cmpd. cmpd. cmpd.

15.0# 05 375 15.05 30. 01 2.0 10-15 125-130 2 Dark amber viscous fluid.15. 0 30. 0 575 15. 0 00.0 4. 0 10-15 125-130 2% Do. 10. 0 40. 0 450 10.0 s0. 0 3. 0 10-15 125-130 3% Do. 5. 0 40. 0 225 5. 0 75. 0 15. 0 10-15125-130 3% Do. 5. 0 75. 0 225 5. 0 00. 0 1s. 0 10-15 125-130 3 Do. 2. 545. 0 113 2. 5 50. 0 20. 0 10-15 125-130 2 Do. 2. 5 50. 0 113 2. 5 70. 02s. 0 10-15 125-130 2% Do. 2. 5 70. 0 113 2. 5 75. 0 30. 0 10-15 125.130 2% Do. 20. 0 0. 0 900 20. 0 50. 0 3. 0 10-15 125-130 3% Do. 10. 030. 0 450 10. 0 00. 0 0. 0 10-15 125-130 2% Do. 10. 0 60. 0 450 10. 000. 0 0. 0 10-15 125-130 2% .Do. 5. 0 45. 0 225 5. o 90. 0 1s. 0 1015125-130 4 Do. 4. 0 72. 0 130 4. 0 s0. 0 20. 0 10-15 125-130 2 Do. 1.030. 0 4. 0 100. 0 25. 0 10-15 125-130 3% Do. 153... 141-... 2.0 50.0 902.0 64.0 32.0 10-15 125-130 3 Do.

' Oxyalkylationsusceptible compound.

ln some instances weights change from gram basis to pound basis. Suchchange in unit is obvious.

- 19 PART As to the use of conventional demii lsifying agents referenceis made to Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part 3. Everything that appears therein applies withequal force and effect to the instant process, noting only that wherereference is made to Example 13b in said text beginning in column andending in column 18, reference should be to Example 6c, hereindescribed.

Having thus described my invention, what I claim as new and desire toobtain by Letters Patent is:

l. The process of breaking petroleum emulsions of the water-invoil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic y p il P c s sa d sy the c hyd p e Pr duc being theproducts resulting-iron; a twoestep manufacturing process consisting offirst condensing (d) an oxyalkylation-susceptible, fusible,non-oxygenated organic solvent-soluble, waten-insoluble, low -sta gephenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over- 6 phenolic nuclei per resin molecule; saidresin being derived by reaction between a difunctional monohydric phenoland an aldehyde having not over 8 carbon atoms and reactive to- Wardsaid phenol; said resin being formed in the substantial absence ofphenols of functionality greater than 2; said phenol ing of the formulain which R is an aliphatic hydrocarbon radical "having at least 4 andnot more than 24 carbon atoms and substituted in the 2,4,6 position; (b)a basic secondary amine free from any primary amino radical having not more than 32 carbon atoms in any group attached to any amino nitrogenradical and reactive towards pyruvic aldehyde; and (c) pyruvic aldehyde;said condensation reaction being conducted at a temperature sufiicientlyhigh to eliminate water andbelow the pyrolytic point of the reactantsand resultants of reaction; and with the proviso that the resinouscondensation product resultingfrom the process be heat-stable andoxyalkylation:susceptible; followed by a second step of reacting saidcondensate with an alpha-beta alkylenfe xide having not more than 4carbon atoms and selected from the class consisting .of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide. V I I i 2.The process of claim 1 with the proviso that there be an alkanol radicalattached to at least one amino nitrogen atom.

3. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyalkylation-susceptible,fusible, non-oxygenated organic solvent-soluble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms andreactive toward said phenol; said resin'being f ormed in the substantialabsence of phenols of functionality greater than 2; saidphenol being ofthe formula 7 in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the'-2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon t m in ny roup attac ed to the amino n tr g n atom andreactive towards pyruvic; aldehyde; and (c) pyruvic aldehyde; saidcondensation reaction being conducted at a temperature sufficiently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by a second step of reacting saidcondensate with an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

4. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding Synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyalkylation-susceptible,fusible, non-oxygenated organic solvent-soluble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms andreactive toward said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than 2; said phenol being ofthe formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atmos and substituted in the 2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any group attached to the amino nitrogen atomand reactive towards pyruvic aldehyde; and (c) pyruvic aldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; with the added proviso that the condensationreaction be conducted so as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule; and with the further proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by a second step of reacting saidcondensate with an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

5. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts beingthe products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyalkylation-susceptible,fusible, non-oxygenated organic solvent-soluble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms andreactive toward said phenol; said resin being tormed in the substantialgames 21 absence of phenols of functionality greater than 2; said phenolbeing of the formula in which R is an aliphatic hydrocarbon radicalhaving at least 4 and not more than 24 carbon atoms and substituted inthe 2,4,6 position; (b) a basic hydroxylated secondary monoamine havingnot more than 32 carbon atoms in any group attached to the aminonitrogen atom and reactive towards pyruvic aldehyde; and (c) pyruvicaldehyde; said condensation reaction being conducted at a temperaturesufliciently high to eliminate water and below the pyrolytic point ofthe reactants and resultants of reaction; with the proviso that thecondensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of apyruvic-aldehyde-derived substituted methylene bridge connecting theamino nitrogen atom with a resin molecule; with the further proviso thatthe ratio of reactants be approximately 1, 2 and 1 respectively; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable and oxyalkylation-susceptible; followedby a second step of reacting said condensate with an alpha-beta alkyleneoxide having not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycideand methylglycide.

6. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyalkylation-susceptible,fusible, non-oxygenated organic solvent-soluble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and an aldehyde having not over 8 carbon atoms andreactive toward said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than said phenol being ofthe formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any group attached to the amino nitrogen atomand reactive towards pyruvic aldehyde; and (c) pyruvic aldehyde; saidcondensation reaction being conducted at a temperature sufliciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule by virtue of a pyruvic-aldehyde-derived substituted methylenebridge connecting the amino nitrogen atom with a resin molecule; withthe added proviso that the ratio of reactants be approximately 1, 2 and1, respectively, with the further proviso that said procedure involvethe use of a solvent; and with the final proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by a second step of reacting saidcondensate with an alpha-beta alkylene 22 oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

7. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyethylation-susceptible,fusible, non-oxygenated organic solvent-soluble, Water-insoluble,low-stage phenol-formaldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and formaldehyde; said resin being formed in thesubstantial absence of phenols of functionality greater than 2; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom and reactive towards pyruvic aldehyde; and (c)pyruvic aldehyde; said condensation reaction being conducted at atemperature sufliciently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of apyruvic-aldehyde-derived substituted methylene bridge connecting theamino nitrogen atom With a resin molecule; with the added proviso thatthe ratio of reactants be approximately 1, 2 and 1, respectively; withthe further proviso that said procedure involve the use of a solvent;and with the final proviso that the resinous condensation productresulting from the process be heat-stable and oxyalkylation-susceptible;followed by a second step of reacting said condensate with an alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide.

8. The process of breaking petroleum emulsions of the Water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufac turingprocess consisting of first condensing (a) anoxytethylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of phenols offunctionality greater than 2; said phenol being of the formula in whichR is an aliphatic hydrocarbon radical having at least 4 and not morethan 14 carbon atoms and substituted in the 2,4,6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms inany group attached to the amino nitrogen atom and reactive towardspyruvic aldehyde; and (c) pyruvic were;

d yd s d on ens o st m; be ng conduc ed a a temperature sufljoientlyhigh to"elimiiiat water" and below the pyrolytic point of the reactantsand resultants of reaction; with the proviso that the condensationreaction be conducted so as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a pyruvic-aldehyde-derivedsubstituted methylene bridge connecting the amino nitrogen atom with aresin molecule; with the added proviso that the ratio of reactants beapproximately 1, 2 and 1, respectively; with the further proviso thatsaid procedure involve the use of a solvent; and with the final provisothat the resinous condensation product resulting from the process beheat stable' and oxyalkylation-susceptible; followed by a second step ofreacting said condensate with an alpha-beta alkylene oxide having'notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

9. The process of breaking petroleum emulsions of the Water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyethylation-susceptible,fusible, non-oxygenated organic solvent-soluble, water-insoluble,low-stage phenol-formaldehyde resin having an average molecular weightcorresponding to at least 3 and not over 5 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and formaldehyde; said resin being formed in thesubstantial absence of phenols of functionality greater than 2; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom and reactive towards pyruvic aldehyde; and (c)pyruvic aldehyde; said condensation reaction being conducted at atemperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of apyruvic-aldehyde-derived substituted methylene bridge connecting theamino nitrogen atom with a resin molecule; with the added proviso thatthe ratio of reactants be approximately 1, 2 and 1, respectively; withthe further proviso that said procedure involve the use of a solvent;and with the final proviso that the resinous condensation productresulting from the process be heatstable and oxyalkylation-susceptible;followed by a second 24 step ofsastin said ondensate w h n alph -betaalkylene oxid'e'haying not more than 4 carbOn atomsand selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide.

10. The process of breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products, said synthetic hydrophileproducts being the products resulting from a two-step manufacturingprocess consisting of first condensing (a) an oxyethylation-susceptible,fusible, non-oxygenated organic solvent, water-insoluble, low-stagephenol-formaldehyde resin having an average molecular weightcorresponding to at least 3 and notover 5 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctionalmonohydric phenol and formaldehyde; said resin being formed in thesubstantial absence of phenols of functionality greater than 2; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in] any group attached tothe amino nitrogen atom and reactive towards pyruvic aldehyde; and (c)pyruvic aldehyde; said condensation reaction being conducted at atemperature above the boiling point of water and below C., with theproviso that the condensation reaction be conducted so as to produce asignificant portion of the resultant in which each of the threereactants have contributed part of the ultimate molecule by virtue of apyruvic-ald myqe-derived substituted methylene bridge connecting theamino nitrogen atom with a resin molecule; with the added proviso thatthe ratio of reactants be approximately 1, 2 and 1, resceptively; withthe further proviso that said procedure involve the use of a solvent;and with the fiinal proviso that the resinous condensation productresulting from the process be heatstable and oxyalkylation-susceptible;followed by a second step of reacting said condensate with an alpha betaalkylene oxide having not more than 4 carbon atoms and selected from theclass consisting of ethylene oxide, propylene oxide, butylene oxide,glycide and methylglycide.

References Cited in the file of this patent UNITED STATES PATENTS2,454,545 Bock et a1. Nov. 23, 1948 2,457,634 Bond 61: a1. Dec. 28, 19482,507,910 Keiser et a1 May 16, 1950 2,558,688 Landa June 26, 19512,589,200 Monson Mar. 11, 1952 2,695,887 De Groote Nov. 30, 1954

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING SYNTHETIC HYDROPHILE PRODUCTS, SAID SYNTHETIC HYDROPHILEPRODUCTS BEING THE PRODUCTS RESULTING FROM A TWO-STEP MANUFACTURINGPROCESS CONSISTING OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE,FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE,LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHTCORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESINMOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONALMONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS ANDREACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIALABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OFTHE FORMULA